Process of producing decorative plastic surfaces



United States Patent 3,129,110 PRQCESS 0F PRODUCING DECORATIVE PLASTIQSURFACES Theodore R. Anderson, Oakland, Caiih, assignor to The GiiddenQornpany, Cieveland, Ohio, a corporation of Ohio No Drawing. lt iiedJuly 31, 1958, Ser. No. 752,299

5 Qlaims. (Cl. 117-67) This invention relates to novel decorativeplastic surfaces and it relates more particularly to a method ofpreparing an irregular and attractive design on a substrate coated witha resinous substance. My invention will be more fully understood byreference to the description in the following specification.

Ever since the advent of gelable polyester resins and their use asdecorative coatings for fiberglass reinforced polyester laminates andthe like, it has been possible to spatter one color of a gelablepolyester resin on a mold and then cover it with a contrasting color ofanother gelable polyester resin. Thus, when the laminate is removed fromthe mold, the spattered color is imprinted on the background colorgiving a multicolor finish to the laminated article.

The above method of obtaining a multicolor finish has a drawback in thatthe spattered gelable polyester resin is very regular in shape; that is,mainly circular, and is, therefore, not as attractive as might bedesired. By the process of my invention, I have been able to provide anirregular and attractive pattern with a spatter coat of a gelablepolyester resin.

It is an object of my invention to provide a method for obtaining anirregular pattern with a spatter coat of a gelable polyester resin.

It is a further object of my invention to provide a novel, decorativefinish on substrates to be coated with known gelable polyester resins.

It is a further object of my invention to provide a method whereby agelable polyester resin is spattered on a substrate to thereby obtain asurface containing a webby appearance and a pattern which is irregularin size and shape.

In accordance with the foregoing, I have found that I can accomplish myobjects by dissolving a polyvinyl acetate resin in a gelable polyesterresin and applying the so-formed solution to a substrate to be coated.Further in accordance with my invention, I apply a catalyzed gelablepolyester resin on the substrate either before or after the spatteredsolution to thereby obtain a unique and attractive coating upon curingsaid coated surface.

As noted above, the two main compositions to be employed in the processof my invention are selected from compositions comprising a resinifiablepolyester resin, which resin can be caused to gel, and a polyvinylacetate resin; all of which compositions have heretofore been known tothe art. In accordance with my invention, I have found that polyvinylacetate resins, especially those of high molecular weight, arecompatible with polyester resins in the liquid state, and that when asolution of the two resins is sprayed on a substrate, a webby decorativeand attractive finish is thereby obtained. Curing of the coating, e.g.by adding accelerators and/or catalysts, at room temperature or at anelevated temperature results in a permanent webby design on the coatedsubstrate.

Polyvinyl acetate resins are well known and so are their methods ofmanufacture. In order, however, to more fully describe this invention, abrief description of two methods of preparing these polyvinyl acetateresins will be described.

One method of preparing a resin of high-molecular weight from vinylacetate is that of suspension polymerization. Suspension polymerizationis achieved by dispersing vinyl acetate in the form of small globules ina non-solvent medium; that is, a liquid carrier which in the case ofvinyl acetate is usually water or an aqueous solution, stronglyagitating the solution and subjecting the vinyl acetate in suspension topolymerizing conditions. The reaction is carried out in the presence ofa vinyl acetate-soluble catalyst and of a suspension stabilizer, thefunction of the latter being to keep the vinyl acetate globulesdispersed during the reaction. Each liquid vinyl acetate globule isconverted into a hard or rubbery bead of polymer. Further detaileddescription of this method can be found in the literature.

The second known method of preparing a polyvinyl acetate resin is thatof emulsion polymerization. This method is based principally on the useof three essential ingredients; that is, emulsifiers, activators andmodifiers. All three ingredients are required for a smooth and rapidconversion of an emulsion of a vinyl acetate into a latex of asubstantially soluble polymer at such low temperatures that the processcan be kept under control and that unwarranted side reactions can beavoided to a suflicient extent. Polymerization by emulsion is usuallycarried out under normal pressures (as is the case with suspensionpolymerization) and in the temperature range of from -20 to 60 C.Emulsion polymerization employs a fine emulsion of oil-soluble vinylacetate in water and initiates the reaction with a system ofWater-soluble catalysts. In emulsion polymerization, a soap isordinarily used as a surfactant and the vinyl acetate/water ratio isordinarily less than that in suspension polymerization. The amount ofsoap or colloid employed is usually within the range of 2-5 percent andthe amount of catalyst about 1 percent.

Although the above description of methods for preparing polyvinylacetate resins is not intended as a detailed and complete teaching, itshould be realized that these methods are well known in the art andfurther reference to the literature can be made for detail.

Many polyvinyl acetate resins are available commercially as proprietaryproducts and in the description of my invention and further in thespecific examples to be given hereafter as illustrations thereof,commercial resins such as Bakelites vinyl acetate resin, Vinylite AYAT,and Shawinigan Products Corporations Gelva resins were employed. TheGelva resins were used because they are available in a very broad rangeof molecular weights and serve to illustrate the range of molecularweights of the polyvinyl acetate resins that can be employed in theprocess of my invention. I have found that polyvinyl acetate resins of amolecular Weight of from about six thousand to nine hundred thousand canbe successfully used in the practice of my invention. Specific referenceto these polyvinyl acetate resins will be made hereinafter.

As is the case of the polyvinyl acetate resins of commerce, the otherresin employed in my invention (that is, the gelable polyester resin) isalso well known to the art.

A polymerizable unsaturated polyester is prepared by reaction of apolyhydric alcohol with ethylenically unsaturated polycarboxylic acid.It is preferable to employ a di-hydric alcohol and a dicarboxylic acidin order to produce a product in which there is a maximum esterificationof the acid and alcohol radicals without excessive viscosity. Ordinarilyit is desirable that the unsaturated polyester be polymerizable into aninfiusible or high melting point resin so that the proportion ofunsaturated components should be such tha tthe polyester contains anaverage of more than one double bond per molecule; for example, theremay be an average of eleven or more double bonds in every ten moleculesof the polyester.

The polymerizable unsaturated polyester can be produced by reaction ofany desired combination of polycarboxylic acid and polyhydric alcohol.For example, an unsaturated dicarboxylic acid such as maleic, fumaric,itaconic, citraconic or mesaconic acid can be reacted with a dihydricalcohol such as my polymethylene glycol in the series from ethyleneglycol to decamethylene glycol, propylene glycol, any butylene glycol,any polyethylene glycol in the series from diethylene glycol tononaethylene glycol, dipropylene glycol, any glycerol monobasic acidmonoester (either in the alpha or beta position), such as monoformin ormonoacetin, any monoether of glycerol with a monohydric alcohol, such asmonomethylin or monoethylin, or any dihydroxy alkane in which thealcohol radicals are primary or secondary or both, in the series fromdihydroxy butane to dihydroxy decane.

Each of such unsaturated dicarboxylic acids contains a polymerizablyreactive A -enedioyl group, and a polymerizable unsaturated polyester oralkyd prepared from any one of such acids, contains a plurality of suchpolymerizably reactive A -enedioyl groups. In other words, each of theacids contains a polymerizably reactive A enoyl group, i.e., a grouphaving the structure III and such groups are contained in dioyl radicalsin the polyester molecule; hence, the dioyl radicals may be defined as A-enedioyl radicals (e.g., butenedioyl or ethenedicarboxylyl radicals).

Instead of a single polycarboxylic acid, a mixture of polycarboxylicacids can be employed, such as a mixture of an unsaturated dicarboxylicacid with a polycarboxylic acid containing more than two acid radicals,such as citric acid. A mixture of polyhydric alcohols can be employed,such as a mixture of dihydric alcohol with a polyhydric alcoholcontaining more than two hydroxyl groups, such as glycerol.

In the preparation of the polymerizable unsaturated polyester, any ofthe usual modifiers such a monobasic acids, monohydric alcohols andnatural resin acids can be added. The larger the proportions ofmonobasic acids and monohydric alcohols, the lower is the average numberof acid and alcohol residues in the resulting polyester molecules, andthe lower is the viscosity of the polyester. On the other hand, the morenearly equal the moleular proportions of dibasic acid and dihydricalcohol, the greater is the average number of residues in the resultingpolyester molecules, and the greater is the viscosity.

The proportions of ingredients used are those proportions that produce apolymerizable polyester of the desired viscosity. Other properties ofthe polyester, such as solubility in various solvents, also can bevaried by selecting various reacting ingredients and varying theirproportions. The infusibility, hardness and inertness of the productobtained by polymerization of the polyester can be increased by varyingthe initial reacting ingredients to increase the average number ofdouble bonds per molecule of the polymerizable polyester.

The point to which the reaction of the ingredients is carried in thepreparation of the polymerizable polyester is simply that point at whichthe product has the desired properties. The consistency or viscosity ofthe polyester varies directly with average number of acid and alcoholresidues in the molecule. For example, the average number of residues inthe molecule of the polyester can vary from about three to about onehundred twenty.

The reaction is carried out at a temperature high enough and for a timelong enough to secure the desired consistency. An elevated temperaturepreferably is employed to expedite the reaction, but during thepreparation of the polyester, the temperature should not be so high northe time of reaction so long as to cause substantial polymerization.There is less danger of premature polymerization if an inhibiting agentis added before the esterification is carried out.

Whenever added, an inhibiting agent is used in the proportion requiredto give the desired degree of inhibiting effect. It may be necessary touse different inhibitors in widely different proportions in order tosecure the same inhibiting effect.

Any desired inhibitor such as hydroquinone, pyrogallol, tannic acid orany aromatic amine, such as aniline or phenylene diamine can be employedas an inhibitor.

The preparation of the unsaturated polyester preferably is carried outin an atmosphere of an inert gas such as carbon dioxide, nitrogen or thelike, in order to prevent darkening or to make it possible to obtain apale or colorless product. Bubbling the inert gas through the reactingingredients is advantageous in that the gas serves the added functionsof agitation and of expediting the removal of water formed by thereaction. Exclusion of oxygen is desirable not only because it causesdiscoloration, but also because it tends to produce prematurepolymerization at the elevated temperatures used.

The acid number of the product depends upon the degree of reaction andthe proportions of acid and alcohol used for the reaction. Withequimolecular proportions of dibasic acid and dihydric alcohol, thereaction can be carried to an acid number of about 20. The use of anacid catalyst can make it possible to attain a lower acid number withoutsubstantial polymerization. Modifications are numerous and includemodification of the unsaturated polyester with saturated alkyd-typeresins, oilmodified alkyd resins, etc. Modification is contemplated alsowith a minor amount of one or more liquid, ethylenically unsaturatedmonomeric materials containing aliphatic carbon-to-carbon unsaturationand compatible and cop-olymerizable with said polyester, e.g., styrene,divinyl benzene, vinyl toluene and other nuclearly-substituted styrenes;diallyl esters such as diallyl phthalate, diallyl succinate, diallylmaleate, diallyl itaconite, etc.; and other unsaturated esters such asdivinyl maleate, dioctyl itaconate, dibenzyl itaconate and the like. Theart of preparing such curable polymerizable materials and theircompositions is well known (as shown by U.S. Patents Nos. 2,420,740,2,453,665, 2,593,787, 2,409,633, 2,433,- 735-2,443,741, 2,450,552,2,255,313, 2,512,410, 2,280,- 256, 2,453,666, 2,510,168, 2,635,089,2,645,626 and U.S. applications Serial No. 523,637, filed July 21, 1955,now abandoned and Serial No. 377,265, filed August 28, 1953, now PatentNo. 2,777,829.

It is well known to those skilled in the unsaturated polyester resin artthat polymerizable polyester liquids can be suitably formulated to becurable to a gelled state in advance of the fully-cured state. Curing ofthe liquids involves exothermic reactions, which exo thermicity tends toaccelerate the reactions. If polymerization is uncontrolled, as by thenon-use of known polymerization stabilizers and/ or inhibitors, thereactive mass cannot be easily kept from proceeding to its fully curedstate, but by including appropriate polymerization stabilizers and/orinhibitors, the mass can be rendered amenable to a gelling treatment inadvance of the final curing treatment. The examples illustrate the useof inhibitors, stabilizers and pigmentation to control the reactivity sothat the desired gelled but uncured state can be attained controllablyin advance of the fully cured state. In general, gelable polyestermasses of the types herein described and illustrated above are 100%polymerizable and are usually mixtures of two or more unsaturatedpolyester types or formulations with polymerizableethylenically-unsaturated monomeric agents containing aliphaticcarbon-to-carbon unsaturation. Nevertheless, a single polyester type orformulation can be used by itself, just as Well. It is more common,though, to mix two or more different ones together since in this way afew stock resin types or formulations can be maintained and from them alarge number of blends can readily be prepared. The stock formulationsare commonly distinguished from each other on the basis of the rigidityor flexibility of the resins they yield. Thus, one might give a flexibleresin, another might give a semi-rigid resin, and a third might give arigid resin. The compositions identified hereinbelow as polyester A,polyester B and polyester C, etc., correspond in principle with thispractice, and their various blends (as in the examples) give curedresinous coatings of various degrees of rigidity, selected for the typeof service for which the finished product is intended. Those skilled inthe art of formulating unsaturated polyester resins recognize that theproportions of saturated carboxylic acids to anti-unsaturated carboxylicacids, the length of the carbon chain(s) involved in the carboxylicacids and in the polyhydric alcohols, the proportion of polyester topolymerizable unsaturated monomer containing aliphatic carbon-to-carbonunsaturation, the degree of functionality in the carboxylic acids andpolyhydric alcohols, and the curing treatment(s), are all factorsaffecting the flexibility and/ or rigidity of the cured resin. Inprinciple, the present invention can be practiced in connection with any100% polymerizable polyester formulation or mixture of formulationswhich can be gelled in an incompletely cured state. As those skilled inthe art are aware, this feature of being gelable without being fullycured can be imparted to any unsaturated polyester mass whether clear orpigmented by incorporating known polymerization catalysts, stabilizersand inhibitors in amounts and proportions which are fixed largely by theparticular polymerizable polyester mass at hand. When that mass ispigmented, particularly with amounts and kinds of pigment which in theaggregate possess what is known in the art as high oil absorption, thena wholly different combination (i.e., kinds and/or amounts) ofpolymerization catalysts, stabilizers and inhibitors is apt to be neededthan if the same polyester mass without any pigment therein were beingformulated to secure the quality of gelability without full curing. Anyof the usual pigments, inert fillers and extenders can be used, but itis desirable that they be free of or contain only small amounts ofreactive metals such as iron, lead, zinc, etc. and/ or their compounds.Some oxides of iron, however, are apparently not reactive in polyesterresins. Thus, I have used both red and black iron oxides with goodresults. Actually, polyesters with black iron oxide have longer storagelife than polyesters with carbon black. Inerts of high oil absorption(e.g. silicates, silica gel) are preferred, only enough high-hidingpigment being used to serve the purpose at hand. In highly pigmentedgelable polyester masses, it is desirable to exclude zinc and leadpigments since they tend to stiffen the resulting mass. This stiffeningeffect is not objectionable in the more fluid, less-highly pigmentedformulations.

In the practice of one embodiment of my invention, I have employedmodified polyester resins of the type described in copending applicationSerial No. 612,072, filed September 25, 1956, now US. Patent No.3,077,424, and that application is incorporated herein by reference. Ingeneral, that copending application describes a method of modifyingpolyester resins of the type described above by imparting hold-outproperties to said resin. The invention described in said copendingapplication provides for the incorporation of certain finely-dividedinorganic solids which modify the rheological characteristics of thepolyester mass toward the characteristics of thixotropy. One suchmaterial is short fiber asbestos of fine standard plastic filler grade.Others include pulverized dehydrated silica gel in an uncompressedstate, e.g. Cab-o-sil, Godfrey L. Cabot Co., PD-244 silica, DavisonChemical Co., or Santocel, Monsanto Chemical Co., certain natural and/ortreated clays which include combined water in their structure (so-calledhydrous clays), e.g. bentonite, etc.

The asbestos shorts, silica gel and hydrous clays are employed in smallamounts usually between about 0.5%

and 10% by weight. Different amounts of each are needed, when usedindividually, to develop optimum hold-out. Where mixtures are used, onemust usually experiment to determine the optimum amount for each of thedifferent mixtures since the effects do not appear to be directlyadditive. It will be noted that each of the three classes of materialsis of hydrous nature, having small amounts of water combined chemicallyinto its make-up, and it is believed that it is the hydrous quality ofeach and the great surface area presented that aids in developing thepresently-desired rheological properties. The silica gels represented byCab-o-sil, Santocel and PD- 244 silica are dry free-flowing powderyproducts which still contain small amounts of combined water in theirgel structure and are submicroscopic particles having an SiO content(dry basis) of 99.099.7%, a free moisture content of 02-20% at C. and anegligible content of CaO, MgO and Fe O (see [1.8. Patents 2,249,767,2,535,063, 2,631,082 and 2,625,492, whose teachings are hereincorporated by reference). Opaline hydrous siliceous minerals such ashyalite and diatomite are natural products comparable to the abovemanufactured products which in comminuted form can also be used if lowin iron oxides. They can be acid washed to lower the iron content.

After the desired rheological properties have been attained as describedunder the preceding heading, finely divided solid materials of a hardabrasive nature are added to impart reinforcement and particularlyskid-proofness. Thus, pulverized sand, pumice, aluminum carbides,aluminum silicides, garnet, glass, porcelain, blast-furnace slag, etc.,represent comminuted abrasive materials which can be used. I especiallyprefer pumice but this preference need not restarin one from practicingthe invention with one or more of the other abrasive materialsidentified above. The pumice (or other abrasive powder) is added to therheologically modified polyester mass in relatively large but uncriticalamounts. Such amounts can range from about 10% to 50% by weight of theunsaturated polyester.

Color pigments and conventional fillers and extenders such as talc,mica, asbestine, sawdust, paper-makers clays, limestone (or other formsof calcium carbonate) can also be included to extend the polyester mass,and where such materials possess a desired color, they impart usefulcolor qualities. Most conventional pigments can be used for color and/orhiding even though a few tend to impede cure of the polyesters.

The methods of preparing gelable polyester resins described in US.Patent 2,817,619 etc., are incorporated herein by reference.

Athough the above description of the resins employed in my invention isdeemed sufficient insofar as the preparation and nature is concerned, itis desirable to point out certain properties of the polyvinyl acetateresins that are of importance to the webbing-gelable coatings of myinvention. Thus, I have found that solutions of polyvinyl acetateresins, especially the higher molecular weight resins, have a strongtendency to string or cobweb when sprayed, and this tendency is stillpresent when the polyvinyl acetate resin is dissolved in a gelablepolyester resin. Thus, upon spraying of a polyester-polyvinyl acetateresin solution, the gelable coating will cobweb.

Polyvinyl acetate resins are compatible with polyester resins while inthe liquid state. When the polyester resin is cured, the polyvinylacetate becomes incompatible, but

In this instance, 86 grams of the resin were added to 1000 ml. ofbenzene at 20 C. and the viscosity in centipoises determined. Suitableresins that can be employed in the process of my invention are thosehaving a viscosity of from 6 to 900 centipoises (and higher) asdetermined by this method. The molecular weight of such resins isapproximately from about six thousand to nine hundred thousand.Shawinigan Corporations Gelva V7 to V800 are suitable polyvinyl acetateresins. In the case of the resins having a viscosity of from 6 to 8centipoises as measured above, a very volatile solvent such as acetonecan be used. However, it is not particularly desirable to employ such avolatile solvent and therefore, I prefer to employ resin solutions of aviscosity, say, of from to 900 centipoises or higher.

In the actual practice of my invention, I have found that the polyvinylacetate-polyester resin webbing solution need not be catalyzed whensprayed on a substrate to be coated. The catalyst contained in thebackground color-imparting gelable polyester resin which is applied overthe sprayed webbing-gelable coat will cure the sprayed resins at thesame time. If the background colorimparting gelable polyester resin isapplied first to the substrate (as in the case of those polyesterscontaining holdout imparting ingredients), then it is only necessarythat the spattered gelable polyester solution be applied (withoutcatalyst, preferably) before the background coat has gelled. In eithercase, the catalyst need only be employed in the coating applied as thebackground, i.e. the non-spattered or non-polyvinyl acetate containingcoat.

As a further explanation of the manipulations deemed necessary in thepractice of my invention the following is offered. When a decorativefinish is desired on a polyester fiberglass laminate or molding, thewebbing-gelable polyester is applied first (usually by spraying) to themold and then the substrate, in this case the laminate, is constructedover the sprayed gelable polyester. When the article is removed from themold, the sprayed webbing gelable polyester that was against the moldwill then be exposed. If both a decorative and protective finish isdesired on polyester fiberglass laminates, wood, concrete, metal, etc.,then a webbing-polyester containing the desired hold-out impartingingredients is applied over the existing substrate. In some cases, e.g.a polyester fiberglass boat, both a webbing-gelable polyester resin(decorative finish) and a webbing-gelable polyester containing hold-outimparting ingredients (decorative and protective finish) can be appliedto a laminate which is a substrate for both of the finishes.

The spatter coat composition consisting of either a decorative or adecorative and protective finish can be pigmented to any desired color.Curing can be afiected at room temperature but also at elevatedtemperatures as will be demonstrated hereinafter.

Curing at elevated temperatures can be varied from 3 hours at 125 to 3to 4 minutes at 250 F. (mold temperature). Thus, it can be seen that abroad range of curing temperatures can be used for polyester resins. Asnoted, catalysts and accelerators can be added in amounts to give theshortest possible curing time while keeping the working life of thepolyester resin long enough to fabricate the article before the resingels.

The amount of catalyst to be employed in the background coat (whetherapplied first or last) can be varied, but usually between about 1 to 2%of methyl ethyl ketone peroxide by weight or equivalent can be employed.The amount of webbing solution, i.e. polyvinyl acetate-polyester resinsolution to be spattered on the substrate can be varied according to thefabricators like etc. or the consumers taste for the particular design.

Also, the proportion or parts by volume or weight of the polyester topolyvinyl acetate can be varied and an excellent webbing solution can beobtained by dissolving one part by volume of polyvinyl acetate to fourparts by volume of polyester solution. After the two resins are asmixed, the resulting solution can be sprayed as is known. The choice ofpolyvinyl acetate resin, the viscosity of the gelable coating and thespraying pressures will affect the pattern of the webbinggelable-coating.

The specific examples offered below demonstrate, but

do not limit, the practice of my invention.

EXAMPLE 1 Part 1 A liquid polyester (designated polyester A) of therigid type was prepared from:

Propylene glycol, industrial 2,960 lbs. Maleic anhydride 1,689 lbs.Phthalic anhydride 2,551 lbs. Xylol 575 lbs. 4-tertiary butyl catechol(as stabilizer) 15 ozs. Stabilizer A 23 lbs. 8 ozs. Rubber grade styrene2,820 lbs.

Total 1,000 gallons.

1 Stabilizer A is prepared by mixing the following: L]

Aeet'amidiue hydrochloride 20 Propylene glycol, ind. grade S0 Themixture is heated to from 1301150 F. to dissolve the components. Thisstabilizer is described and claimed in (:0 pending application SerialNo. 572,192, filed March 19, 1950, now 11.8. Patent No. 2,846,411.

The above ingredients were reacted in the usual manher; that is, thefirst four ingredients were reacted to give a product having an acidnumber of around 50, after which the xylol was stripped off in vacuum.The batch was cooled somewhat and the stabilizers added and thoroughlymixed in. Then after further cooling, the styrene was added. Theresulting solution had a Gardner- Holdt viscosity of U-V at 77 F., andcolor of l2 (Gardner), and acid number of 28-32, and weight of 9.4 lbs.per gallon.

Part 2 A gelable polyester base of a paste consistency was prepared frompolyester A and the following components:

Magnesium silicate (No. 39933) lbs 180 Silica Gel (Cab-o-sil) lbsPolyester A lbs 900 Inhibitor 2 liquid ounces 20 Total gallons-.. 106

The silica gel is a pulverized dehydrated gel in an uncompressed state.

The polymer inhibitor is prepared as follows:

Quinone 0zs. 13 /1 Butyl alcohol pints Styrene (10---- The quinone isadded to the butyl alcohol and styrene and is agitated until dissolved.No heat is used.

All of the above materials are run over a roller mill to a fineness of1-2. A grind gage is used to evaluate the fineness of grind. The grindgage consists of a steel plate containing a wedge shaped channel ofvarious lengths and widths, and ranging from Zero to 0.004 inch indepth. The gage is calibrated to the North standard as follows:

To evaluate the fineness of grind, the gage is laid flat, the deep endis slightly overfiowed with paint. With a scraper the paint is drawntoward the shallow end of the channel. Immediately View the drawdownobliquely and note where the coarse particles appear on the surface ofthe film.

The gelable polyester base is characterized by a weight of 10.65 lbs.per gallon. It can be stored in lined containers.

Part 3 A liquid polyester resin (designated polyester C) of the flexibletype was prepared in a similar manner to polyester A from the followingcomponents:

Diethylene glycol (1.10 mols) 3,587 lbs. Maleic anhydride (0.50 mol)1,507 lbs. Adipic acid (0.50 mol) 2,245 lbs. Xylol (8%) 587 lbs.

Stabilizer A (see polyester A) (0.25% 23 lbs. 4 ozs. 4-tertiary butylcatechol (0.01% (as stabilizer) ozs. Rubber grade styrene (30%) 2,790lbs.

Total 1,000 gallons.

The first four ingredients were reacted to an acid number of about 23,stripped, cooled, the stabilizers added, further cooled and styreneadded. The final product had an acid number of around 15, a color(Gardner) of 23, and a viscosity of DF (Gardner-Holdt) at 77 F. Weight9.3 lbs. per gallon.

Part 4 A black (pigmented) polyester resin concentrate of a liquidconsistency for use in my invention was prepared by first preparing apolyester grinding vehicle as follows:

Propylene glycol, ind. grade (1.13 mols) lbs 2,249 Maleic anhydride(0.50 mol) lbs 1,283 Phthalic anhydride (0.50 mol) lbs 1,938 Xylol (8%)lbs 437 Stablizer A (see polyester A) lbs 25 4-tertiary butyl catechol(0.01%) (as stabilizer) lb 1 Diallyl phthalate monomer (50%) lbs 5,000

Total gallons 1,000

The first four ingredients were charged into a suitable vessel and COwas introduced. The solution was heated to reflux (maximum temperature375 F) and held to an acid number of 50 to 52. The solution was thenvacuum stripped to 100% solids and then cooled to 240 F. Stabilizer Awas then added and mixed for ten minutes. This was then followed with a4-tertiary butyl catechol. The mixture was cooled to 200 F. and thediallyl phthalate was then added slowly and the mixture further cooledand filtered. The final polyester had an acid number of 24-26, a color(Gardner) of 23, a viscosity (Gardner- Holdt) of Z-Z at 77 F. and aweight of 10.0 lbs. per gallon.

In order to form the black pigmented polyester resin concentrate, thefollowing procedure was employed:

Polyester concentrate gallons 85 Black oxide of iron lbs 595 Totalgallons 100 These ingredients were ground to a fineness of 7 on a rollermill. The concentrate had a Weight of 14.4 lbs. per gallon. Thisconcentrate can be packaged in lined containers.

EXAMPLE 2 A black, gelable polyester liquid adapted to be applied to asubstrate, when mixed with a polyvinyl acetate resin 10 (see below) canbe prepared from the above described polyesters of Example 1 as follows:

Polyester base from part 2, Ex. 1 lbs 600' Polyester C from part 3, Ex 1gallons 16 Rubber grade styrene do 20 Black polyester concentrate frompart 4, Ex. 1 lbs 100 Cobalt naphthenate (6% cobalt) gallons 0.75

Total do 100 The above ingredients are mixed to form the pigmentedgelable polyester coat to be applied to the substrate in conjunctionswith polyvinyl acetate resin. The liquid gelable coat is characterizedby a viscosity, full body, of 3000 to 35000 cps. at 77 F. measured witha Brookfield viscosimeter and a weight of 9.95 lbs. per gallon. Theliquid can be catalyzed if desired, although as noted above this is notnecessary, with 2% by weight of Lupersol DDM catalyst. The resulting potlife when catalyzed is about fifteen to twenty minutes.

The polyvinyl acetate resin to be incorporated with the gelablepolyester resin of Example 2 is prepared as follows:

EXAMPLE 3 Rubber grade styrene gallons 80 Polyvinyl acetate resin lbs200 This resin is Bakelite Companys Vinylite AYAT.

The resin is a solid characterized by an intrinsic viscosity incyclohexanone at 20 C. of 0.69, a high softening point and is soluble inketones, aromatics, alcohols, etc.

The solution is prepared by cold cutting the polyvinyl acetate resinwith the styrene, using no heat and good agitation. The solution ischaracterized by a Gardner- Holdt viscosity of U at 77 F., non-volatile25% and a weight of 8.0 lbs. per gallon.

EXAMPLE 4 A Webbing polyester-polyvinyl acetate solution (preferablywithout a catalyst) can then be prepared for application to a substrateby adding one part by volume of the polyvinyl acetate resin solution ofExample 3 to four parts of the gelable polyester solution of Example 2by volume. After mixing, the material is ready to be sprayed, or can bepackaged in lined containers.

Other examples of gelable polyester resins that can be employed eitherto be mixed with the polyvinyl acetate resin or to be used as thebackground coat can be forrnu: lated as follows:

EXAMPLE 5 Part 1 A liquid polyester resin (desi nated polyester B) ofthe semi-rigid type was prepared in a similar manner to polyesters A andC from the following components:

Propylene glycol 2,990 lbs. Maleic anhydride 1,750 lbs. Adipic acid2,610 lbs. Styrene 2,735 lbs. Xylol 588 lbs. 4-tertiary-butyl catechol0.9 lb. Stabilizer A (see polyesterA) 23 lbs. 8 oz.

Part 2 A white gelable polyester resin can be prepared by employingappropriate amount sof the various polyesters. Thus:

Titanium dioxide 3 lbs. 3 ozs. Silica 2 lbs. 5 ozs. Polyester A 4%pints. Polyester B 1% pints. Polyester C 1% pints. Styrene lpint.

Inhibitor of Ex. 1, part 2 A liquid-oz./ gal.

1 1 Additional quinone can be added to the above formulation if desired.

In making the above gelable resin, enough polyester A is added to thefirst two items to make a heavy paste. The mixture is then agitated in aBaker-Perkins agitator for at least an hour until the pigments are wellmixed and then the balance of the resin and styrene is added veryslowly. The mixture is then agitated until uniform. An alternate methodof dispersion is the use of pebble milling of the entire formula fortwelve to sixteen hours.

Part 3 A translucent gelable polyester resin can be prepared by mixingthe following:

Silica 3 lbs. Polyester A pints. Polyester C 2 pints. Styrene lpints.Inhibitor as in part 2 /s liq. oz./gal.

Process as above in part 2.

Examples of other gelable polyester resins can be prepared from theteaching of US. Serial No. 612,072, filed September 25, 1956, referredto above and made a part of this disclosure.

In actual practice I have prepared several very attractive coatings ofvaried cobweb designs by employing combinations of the above notedresins with the gelable polyester resins of Example 5, parts 1 and 2. Ihave employed 1% by weight of methyl ethyl ketone peroxide (60% solutionas is supplied by Lucidol under the trade name of Lupersol DDM). Forcold mold work, 1% by weight of Lupersol DDM and 1 to 2% by weight of anaccelerator i.e. 2% cobalt metal in styrene, is recommended. Dependingon room temperature, the gelable polyester coating will gel in from fiveto fifteen minutes.

For hot molding work (220 to 250 F.), 1% benzoyl peroxide isrecommended. In this instance, when preparing a mold for example, thepolyester will gel almost instantly.

The gelable polyester-polyvinyl acetate resins and the gelable polyesterbackground or color imparting coating of my invention can be applied toa large variety of substrates upon which a decorative coating is desirede.g. metal, wood, ceramics, etc.; or, polyester-fiberglass showerstalls, interior finishes etc.

An attractive laminate can be fabricated by the following example:

(1) A mold is waxed and buffed.

(2) A while spatter coat (not catalyzed) of a webbinggelable polyesterresin is applied to the mold by spraying (decorative finish type).

(3) A black spatter coat as in 2 is then applied.

(4) A pigmented gelable polyester resin (red or any other compatiblecolor) is catalyzed with 2% Lupersol DDM and is applied by spraying(background coat).

(5) The laminate is built up over the red polyester resin coat after thecoat has gelled and started to cure (approximately /2 hour at 75 F.).The laminate consists of a polyester laminating resin reinforced withone layer of fiberglass matt (e.g. 2 ounces) between two layers offiberglass cloth. The polyester resin is catalyzed with 1% Lupersol DDM.

(6) A gray gelable polyester containing hold-out imparting ingredients(background coat) and catalyzed with 2% Lupersol DDM is applied byspraying over the laminate after it has gelled (approximately /2 hour at75 F.).

(7) Black and white spatter coats of webbing-gelable polyester resins(not catalyzed) are then applied by spraying before the background coathas gelled (decorative and protective finish).

(8) The laminate is removed from the mold after an overnight cure atroom temperature.

The above colors were selected at random but the spatter coats andbackground coats can be pigmented to any desired color. The laminate canalso be cured at elevated temperatures. The laminate prepared by theabove series of steps presents an attractive article of manufacture,both sides of the laminate presenting a pleasing and decorative designand finish. Also, as noted, one or more spatter coats of differentcolored webbinggelable polyester resin solutions can be applied to thelaminate, to present a surface of varied and irregular cobweb design.

As will be appreciated from the above description of my invention, afabricator can prepare his own webbing gelable polyester coatingsolutions by using the above mixtures. In the instances where thesubstrate is first sprayed with the webbing solution, no catalyst needbe added to such and it is not necessary that the applicator immediatelyapply the background catalyzed polyester over the sprayed substratesince the sprayed and webbed polyester-polyvinyl acetate can be left onsuch a substrate for periods of time of say from one to two hours beforethe background coat is applied. It is preferred not to wait too longbefore applying the background coat since the styrene (or other monomer)may evaporate from the spatter coat composition (polyester-polyvinylacetate solution) thereby affecting the physical properties of thespatter coat.

When the catalyzed polyester is applied first to the surface, as ispreferred in the case of polyesters comprising ingredients that impartto it hold-out properties, then the polyester-polyvinyl acetate resinsolution must be applied before the solution gels so that both coatingand sprayed resin can be cured simultaneously. It is to be noted thatone of the advantages of this invention is the fact that no catalyst isneeded in the design-imparting cob-webbing solution.

Resort can be had to modifications and equivalents falling within thescope of my invention and the appended claims.

Having thus described my invention, I claim:

1. A process for preparing a decoratively-discontinuous, webby design onthe surface of a substrate, comprising the steps of applying on saidsubstrate a background coat of catalyzed polyester/monomer solutioncharacterized by being substantially polymerizable to a gel state inadvance of the fully cured state, gelling said applied background coat,spraying on said background coat before it has cured a webby deposit ofa homogeneous, compatible solution comprising a gelable substantially100% polymerizable polyester/monomer solution and a web-formingpolyvinyl acetate resin characterized by a molecular weight of at least6000, and curing said polyester/monomer solutions; saidpolyester/monomer solutions being composed essentially of (a) polyhydricalcohol/polycarboxylic acid ester products containing a plurality of A b-enedioyl groups dissolved in (b) liquid monomeric compound which iscopolymerizable with said enedioyl ester products by reason of thepresence of a CH =C group in said monomeric compound.

2. A process as claimed in claim 1 wherein said sprayed solution ispigmented.

3. A process as claimed in claim 2 wherein said background coat ofpolyester/monomer solution contains dispersed therein a small amount offinely-divided solid hydrous inorganic material selected from the groupconsisting of dehydrated silica gel, short asbestos fiber, naturalopaline siliceous minerals, and hydrous clays, said small amount beingeffective to impart holdout properties to said background coat.

4. A process as claimed in claim 1 wherein said background ooat ofpolyester/monomer solution contains dispersed therein a small amount offinely-divided solid hydrous inorganic material selected from the groupconsisting of dehydrated silica gel, short asbestos fiber, naturalopaline siliceous minerals, and hydrous clays, said 13 small amountbeing eifective to impart hold-out properties to said background coat.

5. A process for preparing a decorative resinous laminate fromsubstantially 100% polymerizable polyester/ monomer solutions whichcomprises the steps of (a) contacting with a layer of catalyzed andgelable but uncured polyester/monomer solution a sprayed webby depositof gelable but uncured polyester/monomer solution having dissolvedtherein prior to spraying a Web-forming polyvinyl acetate resin having amolecular weight of at least 6000, and (b) curing said contacting layerand the polyester/monomer solution of said sprayed webby deposit; saidpolyester/monomer solutions being composed essentially of (1) polyhydricalcohol/polycarboxylic ester 14 reason of the presence in the former ofa CH =C group.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Polyester Lacquer Resins, by G. Sprock. Farbe and productscontaining a plurality of A fi-enedioyl groups 15 Lack, pages 181-6,vol. 62 (1956).

dissolved in (2) liquid monomeric compound which is copolymerizable withsaid enedioyl ester products by Finishing Handbook and Directory

1. A PROCESS FOR PREPARING A DECORATIVELY-DISCONTINUOUS, WEBBY DESIGN ONTHE SURFACE OF A SUBSTRATE, COMPRISING THE STEPS OF APPLYING ON SAIDSUBSTRATE A BACKGROUND COAT OF CATALYZED POLYESTER/MONOMER SOLUTIONCHARACTERIZED BY BEING SUBSTANTIALLY 100% POLYMERIZABLE TO A GEL STATEIN ADVANCE OF THE FULLY CURED STATE, GELLING SAID APPLIED BACKGROUNDCOAT, SPRAYING ON SAID BACKGROUND COAT BEFORE IT HAS CURED A WEBBYDEPOSIT OF A HOMOGENEOUS, COMPATIBLE SOLUTION COMPRISING A GELABLESUBSTANTIALLY 100% POLYMERIZABLE POLYESTER/MONOMER SOLUTION AND AWEB-FORMING POLYVINYL ACETATE RESIN CHARACTERIZED BY A MOLECULAR WEIGHTOF AT LEAST 6000, AND CURING SAID POLYESTER/MONOMER SOLUTIONS; SAIDPOLYESTER/MONOMER SOLUTIONS BEING COMPOSED ESSENTIALLY OF (A) POLYHYDRICALCOHOL/POLYCARBOPXYLIC ACID ESTER PRODUCTS CONTAINING A PLURALITY OF$2,3-ENEDIOYL GROUPS DISSOLVED IN (B) LIQUID MONOMERIC COMPOUND WHICH ISCOPOLYMERIZABLE WITH SAID ENEDIOYL ESTER PRODUCTS BY REASON OF THEPRESENCE OF A CH2=C< GROUP IN SAID MONOMERIC COMPOUND.